Particulate fragrance deposition on surfaces and malodour elimination from surfaces

ABSTRACT

Described is a process for imparting a fragrance to, and/or eliminating a malodour from solid or semi-solid surfaces through the use of polymeric particles. The polymeric particles have infrastructures composed of ethylene-vinyl copolymers, polymethyl methacrylate, polystyrene and/or ethylcellulose. Also described are aqueous treatment compositions for use in such processes.

FIELD OF THE INVENTION

Our invention is directed to a process for imparting anaesthetically-pleasing fragrance to, and/or substantially eliminating orcovering a perceived malodour from one or more solid surfaces [forexample, aqueous surfactant-containing composition-treated surfacesincluding fabrics, solid surfaces, mammalian epidermis surfaces, washingand/or conditioning and/or softening of fabrics, by means of carryingout the treatment using either (i) polymeric particles having internalfree volumes which particles optionally contain within their respectivefree volumes controllably-releasable fragrance-imparting and/or malodoursupressing or eliminating or covering compositions in a concentration offrom about 0.5 weight % to about 50 weight % based on particle weight or(ii) an aqueous suspension prepared by causing to be suspended in theaqueous surfactant-containing treatment composition polymeric particleswhich (a) contain within the free volume thereof controllably-releasablefragrance-imparting and/or malodour-supressing or eliminating orcovering compositions in a concentration of from about 0.5 weight % toabout 50 weight % based on particle weight and/or (b) entrap within thefree volume thereof fragrance imparting compositions absorbed from thesurfactant-containing treatment composition for delivery to the surfaceto be treated and/or (c) entrap within the free volume thereof malodourcomponents from the surfaces which are treated.] The fragrance impartingand/or malodour-supressing or eliminating or covering compositionsinitially or subsequently contained within the free volumes of thepolymer particles or malodour molecules initially present on saidsurfaces are compatible with the polymer(s) which make up theinfrastructures of the particles. The polymers which are useful in thepractice of our invention are polyvinyl acetate-ethylene copolymers,ethylcellulose, polystyrene and polymethyl methacrylate. Our inventionis also directed to the novel compositions which comprise theaforementioned polymeric particles in admixture with aqueoussurfactant-containing compositions, including detergents, hair carecompositions, fabric softener compositions and the like.

BACKGROUND OF THE INVENTION

The need for imparting substantive fragrances to, and removing orcovering a perceived malodour from solid or semi-solid surfacesincluding fabric surfaces such as surfaces of articles of clothing beingwashed, the human epidermis, hair follicles and solid surfaces such astile kitchen counters has been, over the past century, well-recognizedin the prior art. Various attempts at fulfilling these needs usingvarious delivery systems have been disclosed in the prior art.

There is a substantial presence in the international market place offabric conditioning sheets containing perfumes intended for delivery tosurfaces, for example, (a) products marketed under the trademarkSNUGGLES (Lever Brothers, New York, N.Y.) described in U.S. Pat. Nos.6,133,226 and 6,297,210 and (b) the products disclosed in publishedapplications for U.S. Patent Applications 2003/0013632 and 2003/0069164.Furthermore, there is a substantial presence in the international marketplace of fabric conditioning liquids containing perfumes for delivery tosolid and/or semisolid surfaces such as fabric surfaces, for example,products marketed under the trademark, DOWNY (Procter & Gamble,Cincinnati, Ohio) and described in U.S. Pat. Nos. 4,424,134 and5,574,179.

The aforementioned published U.S. Patent Application 2003/13632discloses a fabric conditioning article for use in a clothes dryerhaving a flexible sheet and a fabric conditioning composition depositedthereon including a fabric conditioning agent and perfume particleswhich are perfume compositions incorporated into porous mineralcarriers. Other fragrance delivery systems for delivering fragrancecompositions to a surface such as a fabric surface are disclosed inpublished European Patent Application 1 061 124 A1 and published U.S.Patent Application 2002/0016269. In paragraphs 0033 and 0035 ofpublished U.S. Patent Application 2002/0016269 it is stated:

-   -   “[0033] One key embodiment . . . relates to the sustained        release of fragrance on fabric wherein . . . particles are        delivered via fully formulated detergent compositions . . . ”    -   [0035] The particles which comprise the fragrance delivery        systems . . . comprise an polymer or copolymer which can        suitably absorb and deliver the fragrance benefits described        herein to fabric. The . . . resulting polymer has the ability to        carry one or more fragrance raw materials to a fabric and        release said materials once delivered . . . ”

The use of currently-marketed fabric conditioner sheets as exemplifiedherein as well as the uses as set forth in the prior art offragrance-containing particles, for example, particles, theinfrastructures of which are porous mineral materials or cyclodextrins,has, however, been determined to be inadequate for impartingaesthetically pleasing substantive fragrances to, and/or substantiallyeliminating or covering perceived malodours from solid or semi-solidsurfaces such as aqueous surfactant-containing composition-treatedfabrics.

Nothing in the prior art discloses or suggests a method for impartingsubstantive fragrances to, and/or removing or covering perceivedmalodours from solid or semi-solid surfaces using polymeric particleseach of which has a free volume, where the polymers which compose theinfrastructures of the particles are compatible with (a) malodoursubstances absorbable into the particle free volumes, and/or (b)fragrances releasably contained in the free volumes of the particlesand/or (c) fragrances absorbable into the free volumes of the particlesand subsequently releasable therefrom.

SUMMARY OF THE INVENTION

Our invention is directed to a process for imparting anaesthetically-pleasing substantive fragrance to, and/or substantiallyremoving or covering a perceived malodour from one or more solid orsemi-solid surfaces comprising the steps of:

-   -   i. providing a plurality of solid and/or viscoelastic        polymer (a) having a volume average diameter of from about 0.01        microns to about 1000 microns; (b) having a solid infrastructure        which is composed of a substance selected from the group        consisting of an ethylene-vinyl acetate copolymer containing        from about 10% to about 90% vinyl acetate monomeric units, an        ethyl cellulose polymer, a polystyrene polymer and a polymethyl        methacrylate polymer, each of said polymers having a number        average molecular weight of from about 8000 to about 1×10⁶        and (c) having a substantially solid or viscoelastic        three-dimensional porous infrastructure surrounding a free        volume;    -   ii. optionally including in the solid or viscoelastic        infrastructure free volume a fragrance composition, each of the        components of which is compatible with said polymer;    -   iii. effecting deposition of said plurality of polymer particles        onto said surface        wherein fragrance components and malodour molecules are        compatible with said polymer.

Optionally, each of the infrastructures of each of the polymer particlescomprises a filler which creates a diffusion barrier and which increasesthe impact resistance and the modulus of elasticity of each of thepolymer particles. Examples of such fillers are SiO₂, CaCO₃, MgCO₃,Al₂O₃, MgO, ZnO, TiO₂, surface-modified silicas, zeolites (hydratedalkali metal-aluminum silicates), clays, modified clays, wood flour,gypsum (CaSO₄.2H₂O) and activated carbon.

Each of the infrastructures of each of the polymer particles maycontain, in addition, a solvent, for example, one or more of isopropylmyristate, diethyl phthalate, dibutyl phthalate, diisopropyl adipate,benzyl benzoate, mineral oil, a methyl ester of a vegetable-derivedC₁₂-₁₈ carboxylic acid, for example, “soybean methyl ester”, the methylester of a mixture of 26% oleic acid, 49% linleic acid, 11% linolenicacid and 14% saturated fatty acids and a glyceryl ester of avegetable-derived C₁₀ carboxylic acid, preferably the triglyceride of a50:50 mixture of caprylic acid and capric acid marketed under thetrademark, NEOBEE-M5 (Stepan Chemical Company, Northfield, Ill.).

The free volume of a polymer is estimated by comparing the density of acrystalline polymer versus that of the same polymer in the amorphousstate, according to:Free Volume (ml/100 g polymer)=100×[1/ρ_(a)−1/ρ_(c)]where ρ_(a) and ρ_(c) are the densities of the amorphous and crystallineform of the polymer, respectively, since free volume is the space thatcannot be efficiently filled up by a polymer due to its inability topack into a 100% crystalline structure.

For purposes of practicing our invention, “compatibility” which is ameasure of solubility/miscibility and non-reactivity of the fragranceand the polymer is ascertained herein using the following approaches:

(I) Hildebrand or Hansen solubility parameters (group additivity method)as set forth in Barton, “CRC Handbook of Polymer-Liquid interactionParameters and Solubility Parameters”, 1990 by CRC Press, Inc. ISBN0-8493-3544-2 pp. 11-15;

-   -   (2) UNIFAC (Unified quasi chemical theory of liquid mixtures        Functional-group Activity Coefficients “UFAC”) methods which        utilize a group additivity principle by using the groups to add        a non-ideal part to Flory's theory of polymer solubility as set        forth in Gmehling et al., “Vapor-Liquid Equilibria by UNIFAC        Group Contribution. Revision and Extension. 2” Ind. Eng. Chem.        Process. Des. Dev. 1982, 21, 118-27. Furthermore, this method is        based on a statistical mechanical treatment derived from the        quasi chemical lattice model. In addition, this method includes        a combinatorial and a “free volume” contribution (UNIFAC-FV);        and    -   (3) Monte Carlo/molecular dynamics techniques as set forth in        Jacobson, Solomon H. “Molecular Modeling Studies of Polymeric        Transdermal Adhesives: Structure and Transport Mechanisms”        Pharmaceutical Technology, September 1999, pp 120, 122, 124,        126, 128 and 130.

More specifically, our invention provides alternative processembodiments:

-   -   (a) Applying particles each of which has a vacant free volume to        solid or semi-solid surfaces which have adsorbed thereon        malodourous substances. The malodourous substances, being        compatible with the polymer particle infrastructures are        absorbed into the particle free volumes;    -   (b) Placing particles, each of which has a vacant free volume        into an aqueous emulsion containing fragrance substances and        surfactant. The fragrance substances, being compatible with the        polymer particle infrastructures are absorbed, for example,        during storage or treatment, into the particle free volumes, and        subsequently deposited onto solid or semi-solid surfaces such as        fabrics being washed in a washing machine. After the fragrance        deposition, malodour, if present, being compatible with the        polymer, is absorbed into the free volume of the polymer;    -   (c) Placing particles, each of which has a free volume which        contains a compatible fragrance composition, onto a solid or        semi-solid surface. The fragrance composition is released from        the polymer infrastructure and absorbed into the solid or        semisolid surface and/or evolved into the environment        immediately adjacent the solid or semi-solid surface, for        example, the human epidermis or human hair via a hair care        product. After the fragrance deposition, malodour, if present,        being compatible with the polymer, is absorbed into the free        volume of the polymer.

Thus, with respect to the above-mentioned embodiment, (b), our inventionprovides a process for imparting an aesthetically-pleasing substantivefragrance to, and/or substantially removing a perceived malodour fromone or more aqueous surfactant-containing composition-treated solid orsemi-solid surfaces during treatment of said surfaces with one or moresurfactant-containing compositions comprising the steps of:

-   -   i. providing a plurality of polymer particles (a) having a        volume average diameter of from about 0.01 microns to about 1000        microns; (b) having a solid or viscoelastic infrastructure which        is composed of a substance selected from the group consisting of        an ethylene-vinyl acetate copolymer containing from about 10% to        about 90% vinyl acetate monomeric units, an ethylcellulose        polymer, a polystyrene polymer and a polymethyl methacrylate        polymer, each of said polymers having a number average molecular        weight of from about 8000 to about 1×10⁶ and (c) having a        substantially solid or viscoelastic three-dimensional porous        infrastructure surrounding a free volume;    -   ii. providing a surface treatment quantity of an aqueous        composition comprising from about 1% up to about 25% by weight        of at least one surfactant which aqueous composition is designed        to be in intimate contact with said surfaces over a treatment        period of time in a surface treatment concentration and        temperature;    -   iii. providing treatment means for enabling treatment of said        surfaces;    -   iv. introducing (a) said aqueous composition; (b) said surfaces;        and (c) said plurality of particles into said treatment means;    -   v. engaging said treatment means for a treatment period of time        at a treatment temperature;    -   vi. disengaging said treatment means;    -   vii. removing said surfaces from said treatment means;    -   viii. rinsing said surface; and    -   ix. drying said surface        wherein fragrance components of fragrance compositions and        malodour molecules are compatible with said polymers.

In this case, the treatment means is, for example, a washing machine,with the surface to be treated being a fabric being washed. At the endof the washing cycles, that is immediately subsequent to the rinsecycle, the polymer particles complete the release of fragrance onto thesurface of the washed fabric; and, if malodour existed on the fabric,compatible malodour molecules are absorbed into the vacant free volumesof the polymer particles. In the alternative, if the surface is a hairfollicle, the treatment means is a hair washing/rinsing procedure.Immediately subsequent to the rinse cycle, the polymer particlescomplete the release of fragrance onto the surface of each of the washedhair follicles; and, if malodour existed on the hair follicles,compatible malodour molecules are absorbed into the vacant free volumesof the polymer particles. Further in the alternative, if the surface isthe human epidermis, and the treatment means is a bathing procedure, thepolymer particles complete the release of fragrance onto the skinsurface immediately subsequent to rinsing.

The following Table I sets forth publications which disclose fabriccare, hair care and skin care procedures useful in the practice of ourinvention: TABLE I Procedure Type U.S. Pat. No. fabric care 4,318,818fabric care 5,916,862 skin care 6,514,487 hair care 6,544,535 hair care6,540,989 skin care 6,514,489 skin care 6,514,504 skin care and haircare 6,514,918 hard surfaces 6,514,923 fabric care 6,524,494 hair care6,528,046 skin and hair care 6,531,113 skin care 6,551,604 carpet care6,531,437

A preferred process of our invention for imparting anaesthetically-pleasing substantive fragrance to and/or substantiallyremoving a perceived malodour from aqueous surfactant-containingcomposition-treated fabrics, hair follicles, mammalian epidermis orsolid surfaces during treatment of said fabrics or hair follicles ormammalian epidermis or said solid surfaces with surfactant-containingcompositions comprises the steps of:

-   -   i. providing a first plurality of polymer particles (a) having a        volume average diameter of from about 0.01 microns to about 1000        microns, (b) having a solid or viscoelastic infrastructure which        is composed of a an ethylene-vinyl acetate copolymer containing        from about 10% to about 90% vinyl acetate monomeric units and        having a number average molecular weight of from about 8000 to        about 1×10⁶ and (c) having a substantially solid or viscoelastic        three-dimensional porous infrastructure having a free volume        containing a liquid phase fragrance material removably entrapped        in said infrastructure, contained in the interstices of said        infrastructure and outwardly transportable from said        infrastructure, each of the components of which fragrance        material having a C log₁₀ P in the range of from about 1 to        about 7, the initial weight % of fragrance material contained in        said plurality of polymer particles being from about 0.5% to        about 50% by weight of the plurality of polymer particles, each        of said fragrance components being compatible with said polymer;    -   ii. providing a second plurality of polymer particles (a) having        a volume average diameter of from about 0.01 microns to about        1000 microns, (b) having a solid or viscoelastic infrastructure        which is composed of an ethyl cellulose polymer having a number        average molecular weight of from about 8000 to about 1×10⁶        and (c) having a substantially solid or viscoelastic        three-dimensional porous infrastructure surrounding a liquid        phase fragrance material removably entrapped in said        infrastructure, contained in the interstices of said        infrastructure and outwardly transportable from said        infrastructure, each of the components of which fragrance        material having a C log₁₀ P in the range of from about 1 to        about 7, the initial weight % of fragrance material contained in        said plurality of polymer particles being from about 0.5% to        about 50% by weight of the plurality of polymer particles;    -   iii. mixing said first plurality of polymer particles with said        second plurality of polymer particles to form a third plurality        of polymer particles;    -   iv. providing a fabric, hair follicle, mammalian epidermis or        solid surface treatment quantity of an aqueous composition        comprising from about 1% to about 25% by weight of at least one        surfactant which aqueous composition is designed to be in        intimate treatment contact with either (a) at least one fabric        article over a fabric treatment period of time in a fabric        treatment concentration and temperature or (b) at least one        solid surface over a solid surface treatment period of time in a        solid surface treatment concentration and temperature or (c) at        least one hair follicle over a hair follicle treatment period of        time in a hair follicle treatment concentration and temperature        or (d) a mammalian epidermis surface over a mammalian epidermis        surface treatment period of time in a mammalian epidermis        surface treatment concentration and temperature;    -   v. providing treatment means for enabling treatment of said        fabrics, mammalian epidermis, hair follicles or said solid        surfaces;    -   vi. introducing (a) said aqueous composition; (b) said at least        one fabric article, hair follicle, mammalian epidermis or solid        surface; and (c) said third plurality of polymer particles into        said treatment means;    -   vii. engaging said treatment means for a treatment period of        time at a treatment temperature;    -   viii. disengaging said treatment means;    -   ix. removing (a) said at least one fabric article or (b) said at        least one solid surface or (c) said at least one hair follicle        or (d) said mammalian epidermis from said treatment means;    -   x. rinsing (a) said at least one fabric article or (b) said at        least one solid surface or (c) said at least one hair follicle        or (d) said mammalian epidermis; and    -   xi. drying (a) said at least one fabric article or (b) said at        least one solid surface or (c) said at least one hair follicle        or (d) said mammalian epidermis.

The infrastructures of the polymer particles useful in the practice ofour invention may be composed of an ethylene-vinyl acetate copolymercontaining from about 10% to about 90% vinyl acetate monomeric units, anethylcellulose polymer, a polystyrene polymer polymer or a polymethylmethacrylate polymer or the particles may be composed of blends of anyof the foregoing polymers. Preferably, the ethylene-vinyl acetatecopolymers contain from about 65-75% ethylene monomeric moieties andfrom about 25-35% vinyl acetate monomeric moieties. A preferredethylene-vinyl acetate copolymer is ELVAX 260 (E. I. Du Pont de Nemours& Co. Wilmington, Del.) having a melt index of 25 and 28% vinyl acetatemonomeric units. A preferred polystyrene resin useful in the practice ofour invention is STYRON 666D (The Dow Chemical Company, Midland, Mich.)having a melt flow rate of 8.00 g/10 minutes A preferred polymethylmethacrylate resin useful in the practice of our invention is ELVACITE2041 (E. I. Du Pont de Nemours & Co. of Wilmington, Del.) having anumber average molecular weight of 410,000. A preferred ethylcelluloseresin useful in the practice of our invention is ETHOCEL Std.45 (The DowChemical Company, Midland, Mich.) having a viscosity range of 45-55centipoises.

The polymer particles useful in the practice of our invention may beprepared according to a number of processes, for example:

-   (a) The plurality of polymer particles is produced by a process    comprising the sequential steps of (a) blending polymer pellets with    fragrance material for a period of time of from about 0.05 hours to    about 20 hours; (b) extruding the resulting product at a temperature    of from about 130° C. to about 170° C. to form an extrudate; (c)    cooling the resulting extrudate to a temperature in the range of    from about 15° C. to about 40° C. and (d) cryogrinding the resulting    extrudate to form cryoground particles; or-   (b) The plurality of polymer particles is produced by a process    comprising the sequential steps of (a) blending polymer pellets with    silicon dioxide and fragrance material for a period of time of from    about 0.05 hours to about 20 hours; (b) extruding the resulting    product at a temperature of from about 130° C. to about 170° C. to    form an extrudate; (c) cooling the resulting extrudate to a    temperature in the range of from about 15° C. to about 40° C.    and (d) cryogrinding the resulting extrudate to form cryoground    particles;-   (c) The plurality of polymer particles is produced by a process    comprising the sequential steps of (1) extruding polymer pellets    with one or more foam forming agents to from a foamed extrudate; (2)    cooling the resulting extrudate to form an extrudate tow; (3)    particularizing the resulting tow to form microporous polymer    particles; and (4) admixing the resulting particles with a fragrance    composition, the components of which are compatible with the    polymer;-   (d) In the case of using polymer particles, the infrastructures of    which are each composed of polymethyl methacrylate, the polymmethyl    methacrylate polymer particles are produced according to a process    comprising the sequential steps of:    -   (1) milling polymethyl methacrylate to provide polymethyl        methacrylate particles having an average effective diameter in        the range of from about 5 microns to about 100 millimeters; then    -   (2) admixing the resulting particles with a plasticizing        quantity, e.g., from about 50% by weight of the particles to        about 600% by weight of the particles, of a plasticizing        composition which is a lower alkanol such as ethanol, n-propanal        or isoproanol or a lower alkanone such as acetone, methyl ethyl        ketone or methyl isobutyl ketone, or greater than about 10%        aqueous solutions thereof, for example, 25%, 50%, 75% or 95%,        preferably 50% aqueous ethanol solutions for a period of time of        from about 30 seconds to about 10 minutes at a temperature in        the range of from about 20° C. to about 45° C.; then, optionally    -   (3) separating the plasticizing composition from the        thus-treated polymer particles in order to form plasticizing        compound-treated particles, and then, optionally    -   (4) admixing the resulting plasticizing compound-treated polymer        particles with a fragrance material which is compatible with the        polymethyl methacrylate whereby a fragrance composition in a        concentration of from about 0.5% to about 50% by weight of the        filled particles is absorbed into the free volume of the        polymethyl methacrylate polymer particles.

The foregoing polymer particle production processes as well as otherparticle production processes useful for producing polymer particlesuseful in the practice of our invention are set forth in the referenceslisted in the following Table II: TABLE II Polymer Type or PolymerParticle U.S. Pat. No. or Production Type Other Reference Citationethylene-vinyl acetate copolymers(puffed U.S. Pat. No. 4,521,541 usingblowing agent) ethyl cellulose U.S. Pat. No. 6,509,034 polystyrene U.S.Pat. No. 4,247,498 polymethyl methacrylate U.S. Pat. No. 4,247,498

Other particle production processes useful for producing polymerparticles useful in the practice of our invention are set forth in U.S.Pat. Nos. 3,505,432; 4,731,243; 4, 934,609 and 6,213,409.

Each of the efficaciously releasable components of the fragrancecomposition absorbed into the free volumes of the polymeric particlesuseful in the practice of our invention has a C log₁₀ P (calculatedlogarithm of base 10 of the n-octanol/water partition coefficient) ofbetween 1 and 7, according to the inequality: 1≦C log₁₀ P≦7. The rangeof fragrance composition in the polymeric particle is from about 0.5% byweight of the particle to about 45% by weight of the particle. Thevalues of log₁₀ P with respect to fragrance components are discussed indetail in U.S. Pat. Nos. 5,540,853 and 6.451,065 and PublishedApplication 2003/0005522. Specific examples of fragrance componentsuseful in the practice of our invention and the value of the C log₁₀ P'sthereof are as follows: TABLE III Fragrance Component C log₁₀P valuep-t-butyl-α-methylhydrocinnamaldehyde 3.858 (hereinafter referred to asLILIAL (Givaudan-Roure Corporation of Clifton, N.J.)3-methyl-4-(2,6,6-trimethyl-2- 4.309 cyclohexen-1-yl)-3-buten-2-one(Gamma methyl ionone) n-hexyl salicylate 5.260 benzaldehyde 1.480cis-jasmone 2.712 benzophenone 3.120 nerol 2.649 myristicin 3.200 amylsalicylate 4.601 cedryl acetate 5.436 cyclopentadecanolide 6.246 linalylbenzoate 5.233 β-caryophyllene 6.333

Examples of other fragrance components useful in the practice of ourinvention are dihydromyrcenol, a mixture ofhexahydro-4,7-methanoinden-5-yl acetate andhexahydro-4,7-methanoinden-6-yl acetate (CYCLACET (International Flavors& Fragrances Inc., New York, N.Y.)),2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (ALDEHYDE AA (InternationalFlavors & Fragrances Inc., New York, N.Y.)), the methyl ester of3-oxo-2-n-pentylcyclopentane acetic acid (HEDIONE (Firmenich,Incorporated, Plainsboro, N.J.)) andα-methyl-3,4-methylenedioxy-hydrocinnamaldehyde (HELIONAL (InternationalFlavors & Fragrances, New York, N.Y.)).

As illustrated by the graphs in FIGS. 14A and 14B, the process of ourinvention may be operated according to the mathematical model system:$\begin{matrix}{{m_{P}{\int_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}\quad{\mathbb{d}\theta}}}} + {m_{W}{\int_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}\quad{\mathbb{d}\theta}}}} +} \\{m_{S}{\int_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}\quad{\mathbb{d}\theta}}}}\end{matrix} = {C_{T}m_{T}}$for the fragrance composition; and${\sum\limits_{i = 1}^{n}\quad\left( {m_{p} + C_{pi} + {m_{wi}C_{wi}} + {m_{s}C_{si}}} \right)} = {C_{T}m_{T}\quad{for}\quad{``n"}}$individual fragrance components wherein 1≦i≦n

-   wherein θ represents time in hours;-   wherein C_(P) represents the fragrance concentration in the polymer    particle in grams/liter;-   wherein $\frac{\partial C_{P}}{\partial\theta}$    represents the partial derivative of fragrance concentration in the    polymer particle with respect to time, measures in grams/liter-hour;-   wherein C_(w) represents the fragrance concentration in the water    phase in grams/liter;-   wherein $\frac{\partial C_{w}}{\partial\theta}$    represents the partial derivative of fragrance concentration in the    water phase with respect to time measured in grams/liter-hour;-   wherein C_(S) represents the fragrance concentration in the    surfactant phase in grams/liter;-   wherein $\frac{\partial C_{S}}{\partial\theta}$    represents the partial derivative of fragrance concentration in the    surfactant phase with respect to time measured in grams/liter-hour;-   wherein C_(T) represents the total concentration of fragrance in the    system in grams/liter;-   wherein m_(P) represents the mass of the polymer particles in    grams.;-   wherein m_(S) represents the surfactant mass in grams;-   wherein m_(W) represents the water mass in grams; and-   wherein m_(T) represents the total system mass in grams with all    terms being measured at a point in time, θ.

In the mathematical model, $\begin{matrix}{{m_{P}{\int_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}\quad{\mathbb{d}\theta}}}} + {m_{W}{\int_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}\quad{\mathbb{d}\theta}}}} +} \\{m_{S}{\int_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}\quad{\mathbb{d}\theta}}}}\end{matrix} = {C_{T}m_{T}}$as shown in FIG. 14A:C _(P) =−k ₁ LN(θ+1)+k ₂ with 0.015≧k₁≧0.03 and 0.18≧k ₂≧0.22;C _(S) =k ₃ LN(θ+1)+k₄ with 1.5×10⁻¹ ≧k ₃≧2.2×10⁻³ and 1.2×10⁻⁴ ≧k_(4≧2.0×10) ⁻⁴; andC _(W) =k ₅ LN(θ+1)+k ₆ with 1.5×10⁻⁶ ≧k ₅≧3.0×10⁻⁶ and 1.5×10⁻⁷ ≧k₆≧3.0×10⁻⁷

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a polymer particle useful in the practiceof our invention.

FIG. 2 is a group of bar graphs shown in 3 dimensions: nature offragrance evolving material, e.g., polymer or neat fragrance on the “X”axis; number of days of use on the “Y” axis and averaged intensityrating on the “Z” axis.

FIG. 3 is a bar graph chart showing a comparison of % fragrance absorbedfor an ethylene-vinyl acetate copolymer vs. low density polyethylene.

FIG. 4 is a bar graph chart showing a comparison of % preference forneat fragrance vs. ethylene-vinyl acetate copolymer particles containingthe fragrance (150-200 microns mean effective diameter).

FIG. 5 is a bar graph chart showing % fragrance absorption in HTEAQ(hydrogenated triethanolamine ester quaternary ammonium salt base asdescribed in U.S. Application 2003/0069164, e.g., VARISOFT WE-16 (SherexChemical, Inc., Dublin, Ohio) or STEPANTEX VQ-90 (Stepan Company,Northfield, Ill.) for ethylene-vinyl acetate copolymer vs. polystyrenefor various fragrance components.

FIG. 6 is a bar graph chart showing scaled intensity (on a scale of0-10, on the “Y” axis) vs. time (on the “X” axis), comparing fragrancerelease upon soak in an open tub for ethylene-vinyl acetate copolymerparticles (containing a fragrance oil) (150-200 micron particles) vs.neat fragrance oil.

FIG. 7 is a set of graphs for free volume distribution in four polymers:polymethylmethacrylate; polyethylene; polystyrene and ethylene-vinylacetate copolymer (28% vinyl acetate monomeric units) showing volumefraction (on the “Y” axis vs. Voronoi Sphere Volume (measured in cubicangstroms) on the “X” axis).

FIG. 8 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in anethylene-vinyl acetate copolymer (28% vinyl acetate monomeric units),with free energy of mixing in kilojoules/mole on the “Y” axis and weightfraction of fragrance on the “X” axis.

FIG. 9 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolyethylene polymer with free energy of mixing in kilojoules/mole onthe “Y” axis and weight fraction of fragrance on the “X” axis.

FIG. 10 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolymethyl methacrylate polymer with free energy of mixing inkilojoules/mole on the “Y” axis and weight fraction of fragrance on the“X” axis.

FIG. 11 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolystyrene polymer with free energy of mixing in kilojoules/mole on the“Y” axis and weight fraction of fragrance on the “X” axis.

FIG. 12 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-Fy) free energy of mixing of fragrances in anethylcellulose polymer with free energy of mixing in kilojoules/mole onthe “Y” axis and weight fraction of fragrance on the “X” axis.

FIG. 13 is a set of bar graphs shown in eight groups, one for eachfragrance, showing calculated (using UNIFAC-FV) free energy of mixing offragrances in four different polymers with free energy of mixing inkilojoules/mole on the “Y” axis and setting forth fragrance component onthe “X” axis.

FIG. 14A sets forth, for a polymer particle-water-detergent system,graphs of fragrance concentration vs. time (in hours) for polymerparticles initially containing fragrance components in their freevolumes, detergent particles initially not containing any fragrance andfor water initially not containing any fragrance.

FIG. 14B sets forth for a polymer particle-water-detergent system,graphs of fragrance concentration vs. time (in hours) for polymerparticles initially empty (having no fragrance contained in theirrespective free volumes), for detergent particles initially containingfragrance and for water initially not containing any fragrance. Thegraph illustrates a ‘soak-up’ rate for fragrance being absorbed in thepolymer particle free volume.

DETAILED DESCRIPTION OF THE INVENTION

Referring to FIG. 1 the schematic view of a polymer particle 10 usefulin the practice of our invention, the polymer chain is indicated byreference numeral 12 and the fragrance contained in the particle's freevolume is indicated by reference numeral 11.

Referring to FIG. 2, the group of bar graphs shown in 3 dimensions, thenature of fragrance evolving material, e.g., polymer or neat fragranceis shown on the “X” axis indicated by reference numeral 21; the numberof days of use is shown on the “Y” axis indicated by reference numeral22 and the averaged intensity rating is shown on the “Z” axis indicatedby reference numeral 20. The bar graphs for the fragrance-containingethylene-vinyl acetate copolymer 150-200 micron particles (hereinafterreferred to as “EVA particles”) are indicated by reference numerals 23a, 23 b and 23 c for, respectively, days 7, 4 and 0. The bar graphs forfragrance-containing EVA 10-50 micron particles are indicated byreference numerals 24 a, 24 b and 24 c for, respectively, days 7, 4 and0. The bar graphs for the neat fragrance are indicated by referencenumerals 25 a, 25 b and 25 c for, respectively, days 7, 4 and 0.

Referring to FIG. 3, the bar graph chart showing a comparison of %fragrance absorbed (on the “Y” axis, indicated by reference numeral 30)for an ethylene-vinyl acetate copolymer (indicated by reference numeral32) vs. low density polyethylene (indicated by reference numeral 33),with the nature of the polymer set forth along the “X” axis, indicatedby reference numeral 31.

Referring to FIG. 4, the bar graph chart showing a comparison of %preference for neat fragrance (with % preference shown on the “Z” axis,indicated by reference numeral 40) vs. ethylene-vinyl acetate copolymerparticles containing the fragrance (150-200 microns mean effectivediameter), the bar graph for neat fragrance is shown by referencenumeral 42 and the bar graph for the EVA particles is shown by referencenumeral 43. The fragrance emitting substance is shown along the “X”axis, shown by reference numeral 41.

Referring to FIG. 5 a bar graph chart showing % fragrance absorption(shown on the “Y” axis, indicated by reference numeral 50) in HTEAQ basefor ethylene-vinyl acetate copolymer vs. polystyrene for variousfragrance components (shown along the “X” axis, indicated by referencenumeral 51). The reference numerals for each fragrance component isgiven in the following Table IV: TABLE IV Fragrance Component EVAPolystyrene ethyl-2-methyl valerate 52a 52b limonene 53a 53bdihydromyrcenol 54a 54b β-phenylethyl alcohol 540a  540b  benzyl acetate55a 55b geraniol 56a 56b dimethyl benzyl carbinyl 57a 57b acetate methylnonyl acetaldehyde 58a 58b CYCLACET 59A 59B 2-methoxynaphthalene 560a 560b  β-ionone 561a  561b  LILIAL 562a  562b  n-hexyl salicylate 563a 563b  TONALID (6-acetyl- 564a  564b  1,1,3,4,6,6-hexamethyltetrahydronaphthalene (PFW Chemicals B.V., Barneveld, Netherlands))

Referring to FIG. 6, a bar graph chart showing scaled intensity (on ascale of 0-10, on the “Y” axis, indicated by reference numeral 60) vs.time (on the “X” axis shown by reference numeral 61), comparingfragrance release upon soak in an open tub for ethylene-vinyl acetatecopolymer particles (containing a fragrance oil) (150-200 micronparticles) vs. neat fragrance oil each member of each group of bargraphs is indicated by a reference numeral as shown in Table V: TABLE VTime EVA Neat Fragrance Oil Powder (−1 hour) 62b 62a Dissolution (0hours) 63b 63a  1 hour 64b 64a  2 hours 65b 65a  4 hours 66b 66a  8hours 67b 67a 24 hours 68b 68a

Referring FIG. 7, it is a set of four graphs for free columndistribution in four polymers: polymethylmethacrylate (reference numeral75 with illustrative data point 75 a); polyethlene (reference numeral 72with illustrative data point 72 a); polystyrene (reference numeral 74with illustrative data point 74 a) and ethylene-vinyl acetate copolymer(28% vinyl acetate monomeric units) (reference numeral 73 withillustrative data point 73 a) showing volume fraction (on the “Y” axisshown by reference numeral 70) vs. Voronoi Sphere Volume (measured incubic angstroms) on the “X” axis (shown by reference numeral 71).

Referring to FIG. 8, it is a set of 8 graphs, one for each fragrancecomponent, showing calculated (using UNIFAC-FV) free energy of mixing offragrances in an ethylene-vinyl acetate copolymer (28% vinyl acetatemonomeric units), with free energy of mixing in kilojoules/mole on the“Y” axis (indicated by reference numeral 80) and weight fraction offragrance on the “X” axis (indicated by reference numeral 81). Thereference numerals defining each graph is shown in a table for FIGS.8-12, inclusive, in Table VI.

FIG. 9 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolyethylene polymer with free energy of mixing in kilojoules/mole onthe “Y” axis (indicated by reference numeral 90) and weight fraction offragrance on the “X” axis (indicated by reference numeral 91). Thereference numerals defining each graph is shown in a table for FIGS.8-12, inclusive, in Table VI.

FIG. 10 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolymethyl methacrylate polymer with free energy of mixing inkilojoules/mole on the “Y” axis (indicated by reference numeral 100) andweight fraction of fragrance on the “X” axis (indicated by referencenumeral 101). The reference numerals defining each graph is shown in atable for FIGS. 8-12, inclusive.

FIG. 11 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in apolystyrene polymer with free energy of mixing in kilojoules/mole on the“Y” axis (indicated by reference numeral 110) and weight fraction offragrance on the “X” axis (indicated by reference numeral 111). Thereference numerals defining each graph is shown in a table for FIGS.8-12, inclusive.

FIG. 12 is a set of 8 graphs, one for each fragrance component, showingcalculated (using UNIFAC-FV) free energy of mixing of fragrances in anethylcellulose polymer with free energy of mixing in kilojoules/mole onthe “Y” axis (indicated by reference numeral 120) and weight fraction offragrance on the “X” axis (indicated by reference numeral 121). Thereference numerals defining each graph is shown in a table for FIGS.8-12, inclusive. TABLE VI Polymethyl- Ethyl Fragrance Polyethylenemethacrylate Polystyrene Cellulose Component EVA (FIG. 8) (FIG. 9) (FIG.10) (FIG. 11) (FIG. 12) Dihydromyrcenol 85 94 102 113 128 LILIAL 87 98108 115 125 CYCLACET 84 97 107 118 129 ALDEHYDE 83 96 105 117 124 AAγ-methyl 88 — 106 116 122 ionone n-hexyl 82 93 103 112 126 salicylateHEDIONE 89 95 107 119 127 HELIONAL 86 92 104 114 123

Referring to FIG. 13, it is a set of bar graphs shown in eight groups,one for each fragrance, showing calculated (using UNIFAC-FV) free energyof mixing of fragrances in an four different polymers with free energyof mixing in kilojoules/mole on the “Y” axis (indicated by referencenumeral 130) and setting forth fragrance component on the “X” axis(indicated by reference numeral 131). Reference numerals for each groupof bar graphs and for each bar graph in each group for each fragrancecomponent are set forth in the following Table VII: TABLE VII FragranceGroup Polymethyl- Component of Bar Graphs EVA methacrylate polystyreneethyl cellulose Dihydromyrcenol 132 132a 132b 132c 132d LILIAL 133 133a133b 133c 133d CYCLACET 134 134a 134b 134c 134d ALDEHYDE 135 135a 135b135c 135d AA γ-methyl 136 136a 136b 136c 136d ionone n-hexyl 137 137a137b 137c 137d salicylate HEDIONE 138 138a 138b 138c 138d HELIONAL 139139a 139b 139c 139d

Referring to FIG. 14A, it sets forth, for a polymerparticle-water-surfactant system, graphs of fragrance concentration (onthe “Y” axis, indicated by reference numeral 140) vs. time (in hours)(on the “X” axis indicated by reference numeral 141) for polymerparticles initially containing fragrance components in their freevolumes (the graph being indicated by reference numeral 142 with a datapoint a 0 hours being indicated by reference numeral 152 and with a datapoint at about 150 hours being indicated by reference numeral 142 a),surfactant phase (e.g., containing micelles and/or vesicles) initiallynot containing any fragrance (the graph being indicated by referencenumeral 143 with a data point at about 150 hours being indicated byreference numeral 143 a) and for water initially not containing anyfragrance (the graph being indicated by reference numeral 144 with adata point at about 150 hours being indicated by reference numeral 144a). Line 150 represents a concentration of about 8%, as asymptoteapproached by the fragrance concentration in the polymer particle atθ=∞. Line 151 represents an asymptote approached by fragranceconcentration in the surfactant phase (considerably less than 8%) atθ=∞.

Referring to FIG. 14B, it sets forth for a polymerparticle-water-surfactant system, graphs of fragrance concentration (onthe “Y” axis, indicated by reference numeral 140) vs. time (in hours)(on the “X” axis, indicated by reference numeral 141) for polymerparticles initially empty (having no fragrance contained in theirrespective free volumes) (the graph being indicated by reference numeral145, with a data point at about 150 hours being indicated by referencenumeral 145 a), for surfactant phase (e.g., containing vesicles and/ormicelles) initially containing fragrance (the graph being indicated byreference numeral 146 with a data point at 0 hours being indicated byreference numeral 153 and a data point at about 150 hours indicated byreference numeral 146 a) and for water initially not containing anyfragrance (the graph being indicated by reference numeral 147 with adata point at about 150 hours being indicated by reference numeral 147a). The graph illustrates a ‘soak-up’ rate for fragrance being absorbedin the polymer particle free volume. Line 154 represents a concentrationof about 8%, an asymptote approached by the fragrance concentration inthe polymer particle at θ=∞.

All U.S. Patents and Patent Applications described herein areincorporated by reference as if set forth in their entirety.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention, which is only limited bythe claims as set forth. Unless noted to the contrary, all percentagesare weight percent unless noted to the contrary.

EXAMPLE A

The following fragrance is prepared for use in conjunction with thefollowing Examples 1-6: Ingredient Parts by Weight HEDIONE 50 LILIAL 50γ-methyl ionone 50 dihydromyrcenol 50 n-hexyl salicylate 50 ALDEHYDE AA50

EXAMPLE I

Two groups of particles of the ethylene-vinyl acetate copolymer, ELVAXdescribed in detail, herein, were milled to (a) an average effectivediameter of 150-200 microns (Group A) and (b) an average effectivediameter of 10-50 microns (Group B) in liquid nitrogen using theapparatus and technique as described in U.S. Pat. No. 4,731,243. In eachof Groups A and B, 300 cc. of the fragrance of Example A was admixedwith 100 grams of the milled ethylene-vinyl acetate copolymer, withstirring at 50 rpm, for a period of 12 hours at 28° C. The resultingproducts were then admixed with the fabric conditioner, DOWNY FREE &SENSITIVEP(Procter & Gamble Company, Cincinnati, Ohio) to a finalfragrance level of 1% and allowed to equilibrate at room temperature fora period of 168 hours. The resulting fabric conditioner compositionswere used to wash towels in a standard wash cycle followed by machinedrying for one drying cycle at medium/high. The dried towels wereevaluated on a scale of 0 to 5 for fragrance intensity (with 5 being thegreatest fragrance intensity, and 0 showing no perception of fragrance)and compared to a control that was washed using the same fabricconditioner admixed with the neat fragrance of Example A at a fragrancelevel of 1%. The towels were aged at room temperature on open shelvesand evaluated over a 1 week period. The results are set forth in FIG. 2described above. FIG. 2 indicates the two fold superiority over the oneweek period of the use of the 150-200 micron particles of our inventionand the 1.5 fold superiority of the 10-50 micron particles of ourinvention vs. the use of the neat fragrance.

Substantially identical results were achieved when, in place of theparticles having the ethylene-vinyl acetate copolymer infrastructure,particles having an infrastructure composed of ETHOCEL Std.45 were used.

EXAMPLE II(A)

Three groups of unfragranced particles having vacant free volumesdesignated A, B and C of the ethylene-vinyl acetate copolymer, ELVAXdescribed above were milled to an average effective diameter of 150-200microns in liquid nitrogen using the apparatus and technique asdescribed in U.S. Pat. No. 4,731,243. Similarly, three groups ofunfragranced particles, designated D, E and F of the ethylcellulosepolymer, ETHOCEL Std.45 described above were milled to an averageeffective diameter of 150-200 microns in liquid nitrogen using theapparatus and technique as described in U.S. Pat. No. 4,731,243.Similarly, one group of unfragranced particles, designated G of lowdensity polyethylene and one group of unfragranced particles designatedH of high density polyethylene were milled to an average effectivediameter of 150-200 microns. Groups A, B, D, E, G and H particles wereadded to an ALL (Lever Brothers Company, Edgewater, N.J.) fabricconditioner formulation which contains fragrance. In addition groups Cand F were added to DOWNY fabric conditioner base which containsfragrance. In every case, the amount of fragrance absorbed wasquantitated via GC analysis after filtration and solvent extraction ofthe particles. The ethylene-vinyl acetate copolymer and the ethylcellulose polymer were ascertained to absorb the fragrance significantlywith dependence on the chemical nature of the fragrance molecules aswell as the nature of the softener formulation, while particles havingan infrastructure composed of low density polyethylene or high densitypolyethylene absorb indignificant amounts of individual fragrancecomponents. The following table VIII indicates the results on which theforegoing conclusions are based: TABLE VIII ALL ALL Fabric Fabric DOWNYFragrance Con- Con- Fabric Polymer component ditioner ditionerConditioner ethylene-vinyl Group A Group B Group C acetate copolymerethylene-vinyl dihydromyrcenol 1.7% 1.5% 0.1% acetate copolymerethylene-vinyl ALDEHYDE AA 2.2% 1.6% 0.2% acetate copolymerethylene-vinyl CYCLACET 5.3% 5.4% 0.5% acetate copolymer ethylene-vinylLILIAL 5.1% 5.4% 0.4% acetate copolymer ethylene-vinyl HEDIONE 4.7% 4.8%0.4% acetate copolymer ethylene-vinyl TOTAL 18.9% 18.7% 1.6% acetatecopolymer ethyl cellulose Group D Group E Group F polymer ethylcellulose dihydromyrcenol 2.9% 2.0% 0.4% polymer ethyl celluloseALDEHYDE AA 2.4% 1.4% 0.5% polymer ethyl cellulose CYCLACET 6.6% 5.3%0.9% polymer ethyl cellulose LILIAL 6.3% 5.6% 0.6% polymer ethylcellulose HEDIONE 6.0% 5.4% 0.9% polymer ethyl cellulose TOTAL 24.2%19.7% 3.3% polymer Low Density Group G Polyethylene Low Densitydihydromyrcenol 0.1% Polyethylene High Density Group H Polyethylene HighDensity ALDEHYDE AA 0.1% Polyethylene High Density CYCLACET 0.1%Polyethylene High Density LILIAL 0.1% Polyethylene High Density HEDIONE0.1% Polyethylene

EXAMPLE II(B)

A group of unfragranced particles having vacant free volumes designatedJ of the ethylene-vinyl acetate copolymer, ELVAX described in detailabove were milled to an average effective diameter of 150-200 microns inliquid nitrogen. 100 grams of the particles were added to the 200milliliters of the fabric conditioner base DOWNY. The resulting mixturewas used to wash fabrics in a washing machine. The resulting washedfabric was dried in an automatic dryer. The dried laundry was found tohave a significant increase in fragrance intensity vs. a substantiallyidentical batch of fabrics washed and dried using the same fabricconditioner base and an equivalent amount of neat fragrance (preparedaccording to Example A herein) as opposed to fragrance contained inparticle free volumes.

In addition, fabrics which were washed with the particle-containingsoftener, DOWNY, (containing fragrance) and then line-dried werepreferred greater than about 70% of the time, repeatedly by a group of10 panelists in a double blind study vs. a control which was, DOWNY FREE& SENSITIVE with added neat fragrance (the fragrance of Example A,herein) at the same level, that is 1% weight:weight. Similar resultswere obtained using other fabric softener products, when the particlesof the present invention were utilized compared to the control.

EXAMPLE III

A group of particles designated K of the ethylene-vinyl acetatecopolymer, ELVAX described above were milled to an average effectivediameter of 150-200 microns in liquid nitrogen using the apparatus andtechnique described above. A second group of particles, designated L oflow density polyethylene were milled to an average effective diameter of150-200 microns in liquid nitrogen. Each of particle groups K and L, inthe amounts of 100 grams was added to separate 200 gram samples of TIDE(Procter & Gamble Company, Cincinnati, Ohio) detergent powder asdescribed in U.S. Pat. Nos. 4,318,818 and 5,916,862 and the resultingmixtures were each placed in a separate jar, after dry-blending of themixtures. To each jar, in a concentration of 16.7% by weight of theresulting mixture, the Fragrance formulation of Example A was added.Each jar was sealed and shaken. 35 Grams of each of the contents ofeachjar was then separately added to one liter of water with stirring for aperiod of 120 seconds, thus enabling the detergent part of each mixtureto dissolve, while the polymer particles remained undissolved. Thepolymer particles were then removed from each mixture by means offiltration and analyzed via solvent extraction followed by gaschromatography of the resulting extracts in order to determine theamount of fragrance absorbed in the free volumes of the respectivepolymers of Groups K and L. As shown in the bar graphs of FIG. 3, theparticles having the infrastructure composed of the ethylene-vinylacetate copolymer were found to absorb a significant amount (29%) offragrance from the system, whereas the low density polyethylene absorbedsubstantially no fragrance.

Accordingly, it is appropriate to conclude that the ethylene-vinylacetate copolymer particles having an average effective diameter of150-200 microns can be utilized to soak up compatible fragrance frompowder laundry detergent so that when the detergent is used to washclothing the particles will deposit on the cloth and release a pleasingodor for relatively long periods of time; greater than about a week.

EXAMPLE IV

700 Grams. of unground ethylene-vinyl acetate copolymer pellets havingan average effective diameter of 0.5 cm. (ELVAX) were blended with 100grams. silicon dioxide and 200 grams of the fragrance of Example A. Theblending was carried out by placing the ingredients in a 1500 cc. sealedjar and placing the jar on a rotating mixer at 20 revolutions per minutefor a period of 12 hours. The resulting pellets, containing soaked-upfragrance, were then fed into a twin barrel extruder with the barrelspre-heated to 150° C., thereby producing a homogeneous molten extrudate.The molten extrudate tow on leaving the extruder was cooled to roomtemperature and fed into a coarse grinder, and then into a grinder whilecooling the particles using liquid nitrogen.

The resulting particles were admixed with TIDE FREE detergent powder(not containing any fragrance) and the resulting mixture was blended ina solids mixer at 35 rpm. The resulting blend was used in a handwashapplication. Upon addition of the resulting mixture to a bucket of watercontaining dirty laundry, the detergent dissolved and the remainingparticles having infrastructures composed of the ethylene-vinyl acetatecopolymer floated to the surface. The exposure of the particles to wateraltered the thermodynamic balance thereby triggering greater release offragrance as shown in FIG. 6. After 1 hour, the aroma in the environmentproximate the bucket reached a maximum intensity, and then stabilized.The resulting aroma masked the malodour that developed upon soaking andincreased the perception of cleanliness and freshness of the wash.Accordingly, it can be properly concluded that the particles havinginfrastructures composed of the ethylene-vinyl acetate copolymer can beused in laundry handwash to mask the malodour that develops over aperiod of time when laundry is left to soak for long periods of time,such as greater than 8 hours.

A second experiment was then carried out whereby an ethylcellulose basedparticle, ETHOCEL Std.45 described above was then substituted for theethylene-vinyl acetate copolymer particle. In all other respects, theconditions were identical. The ethylcellulose particles were found torelease the fragrance 50% faster during the first two hours, thusproviding a “burst” effect; and subsequently had a significantly lower(50%) release rate.

A third experiment was then carried out whereby a low densitypolyethylene (LDPE) particle was then substituted for the ethylene-vinylacetate copolymer particle. In all other respects, the conditions wereidentical. The LDPE particles did not release any fragrance and showedno benefit in the application.

EXAMPLE V

Malodour Absorption

A group of particles designated M having infrastructures composed of theethylene-vinyl acetate copolymer, ELVAX described above were milled toan average effective diameter of 200 microns in liquid. At the rate of1%, the resulting particles were added to a 10 ppm aqueous isovalericacid (malodour) solution. After 1 minute, the malodour in the headspaceabove the solution was significantly reduced vs. the control, which hadno particles, but was free isovaleric acid in a concentration of 10 ppm.Using HPLC, it was ascertained that at the rate of 1% the particleshaving an infrastructure composed of ethylene-vinyl acetate copolymerwill absorb 70 parts per million (ppm) isovaleric acid from a solutionhaving a concentration of isovaleric acid of 186 ppm.

EXAMPLE VI Preparation of Polymethylmethacrylate Particles ContainingSubstantial Free Volumes

500 Grams. of polymethyl methacrylate unground pellets (ELVACITE 2041were milled to an average effective diameter of 100 microns in liquidnitrogen. The milled product was divided into ten 50 gram portionsdesignated: A, B, C, D, E, F, G, H, I and J.

At 25° C., portion A is submerged in 300 ml. of the fragrance preparedaccording to Example A, with stirring a 60 rpm for a period of 10minutes. No fragrance was absorbed into the particles.

Portion B was heated to 105° C. under a nitrogen atmosphere.Simultaneously, 300 ml. of fragrance prepared according to Example A washeated to 50° C. under 2 atmospheres nitrogen pressure, with stirring at60 rpm. The heated polymethyl methacrylate particles were then submergedin the fragrance with stirring at 60 rpm, for a period of 10 minuteswhile maintaining the pressure at 2 atmospheres nitrogen. No fragrancewas absorbed into the particles.

Portions C, D, E and F were separately admixed, each with 50 cc. of,respectively, 95%, 75%, 50%, and 25% aqueous ethanol, and each of theresultant slurries was stirred at 25° C. at 60 rpm for a period of 60seconds. In each case, particles were separated from the aqueous ethanolby means of filtration. Each of the resulting particle groups was thensubmerged, with stirring at 60 rpm in 300 ml. fragrance preparedaccording to Example A for a period of 60 seconds. In each case theparticles absorbed fragrance to 45% by weight of the final particle.

Portions G, H, I and J were separately admixed, each with 50 cc. of,respectively, 95%, 75%, 50%, and 25% aqueous ethanol, and each of theresultant slurries was stirred at 25° C. at 60 rpm for a period of 60seconds. In each case, particles were separated from the aqueous ethanolby means of filtration. Each of the resulting particle groups was thensubmerged, with stirring at 60 rpm in 300 ml. fragrance preparedaccording to Example A for period of 300 seconds. In each case theparticles absorbed fragrance to 50% by weight of the final particle.

1. A process for imparting an aesthetically-pleasing substantivefragrance to, and/or substantially removing a perceived malodour fromone or more aqueous surfactant-containing composition-treated solid orsemi-solid surfaces during treatment of said surfaces with one or moresurfactant-containing compositions comprising the steps of: i. providinga plurality of polymer particles (a) having a volume average diameter offrom about 0.01 microns up to about 1000 microns; (b) having a solid orviscoelastic infrastructure which is composed of a substance selectedfrom the group consisting of an ethylene-vinyl acetate copolymercontaining from about 10% to about 90% vinyl acetate monomeric units, anethylcellulose polymer, a polystyrene polymer and a polymethylmethacrylate polymer, said polymers having a number average molecularweight of from about 8000 to about 1×10⁶ and (c) having a substantiallysolid or viscoelastic three-dimensional porous infrastructuresurrounding a free volume; ii. providing a surface treatment quantity ofan aqueous composition comprising from about 1% to about 25% by weightof at least one surfactant which aqueous composition is designed to bein contact with said surfaces over a treatment period of time in asurface treatment concentration and temperature; iii. providingtreatment means for enabling treatment of said surfaces; iv. introducing(a) said aqueous composition; (b) said surfaces; and (c) said pluralityof particles into said treatment means; v. engaging said treatment meansfor a treatment period of time at a treatment temperature; vi.disengaging said treatment means; vii. removing said surfaces from saidtreatment means; viii. rinsing said surface; and ix. drying said surfacewherein fragrance components of fragrance compositions and malodourmolecules are compatible with said polymers.
 2. The process of claim 1wherein each of the free volumes of each of the polymer particlesprovided is initially empty and, during storage or treatment of saidsurfaces, absorbs components from said aqueous surfactant-containingcomposition and effects deposition of said fragrance components ontosaid surfaces.
 3. The process of claim 1 wherein each of the freevolumes of each of the polymer particles provided is initially empty,and during treatment, encapsulates malodourous components from saidsurfaces.
 4. A process for imparting an aesthetically-pleasingsubstantive fragrance to, and/or substantially removing a perceivedmalodour from one or more aqueous surfactant-containingcomposition-treated solid or semi-solid surfaces during treatment ofsaid surfaces with one or more surfactant-containing compositionscomprising the steps of: i. providing a plurality of solid and/orviscoelastic polymer particles (a) having a volume average diameter offrom about 0.01 microns to about 1000 microns; (b) having a solidinfrastructure which is composed of a substance selected from the groupconsisting of an ethylene-vinyl acetate copolymer containing from about10% to about 90% vinyl acetate monomeric units, an ethylcellulosepolymer, a polystyrene polymer and a polymethyl methacrylate polymer,each of said polymers having a number average molecular weight of fromabout 8000 to about 1×10⁶ and (c) having a substantially solid orviscoelastic three-dimensional porous infrastructure surrounding a freevolume; ii. admixing said solid or viscoelastic polymer particles withsolid phase surfactant particles whereby a polymer-surfactant mixture isformed; iii. admixing the resulting polymer-surfactant mixture withwater thereby forming an aqueous surfactant composition comprising fromabout 1% to about 25% by weight of said surfactant which aqueouscomposition is designed to be in contact with said surfaces over atreatment period of time in a surface treatment concentration andtemperature; iv. providing treatment means for enabling treatment ofsaid surfaces; v. introducing (a) said aqueous surfactant compositionand (b) said surfaces into said treatment means; vi. vii. engaging saidtreatment means for a treatment period of time at a treatmenttemperature; viii. disengaging said treatment means; ix. removing saidsurfaces from said treatment means; x. rinsing said surface; and xi.drying said surface wherein fragrance components and malodour componentsare compatible with said polymers.
 5. The process of claim 4 whereineach of the free volumes of each of the polymer particles provided isinitially empty and, during storage or treatment of said surfaces,encapsulates components from said aqueous surfactant-containingcomposition and effects deposition of said fragrance components ontosaid surfaces.
 6. The process of claim 4 wherein each of the freevolumes of each of the polymer particles provided is initially empty,and during treatment, absorbs malodourous components from said surfaces.7. The process of claim 4 wherein said surface is selected from thegroup consisting of a fabric surface and a hair follicle surface andsaid treatment is a washing treatment.
 8. The process of claim 4 whereinsaid surface is a fabric surface, said surfactant is a detergent andsaid treatment is a washing treatment.
 9. The process of claim 1 forimparting an aesthetically-pleasing substantive fragrance to and/orsubstantially eliminating a perceived malodour from aqueoussurfactant-containing composition-treated fabrics, hair follicles,mammalian epidermis or solid surfaces during treatment of said fabrics,hair follicles, mammalian epidermis or solid surfaces withsurfactant-containing compositions comprising the steps of: i. providinga plurality of polymer particles (a) having a volume average diameter offrom about 0.01 microns to about 1000 microns, (b) having a solid orviscoelastic infrastructure which is composed of a substance selectedfrom the group consisting of an ethylene-vinyl acetate copolymercontaining from about 10% to about 90% vinyl acetate monomeric units, apolystyrene polymer, a polymethyl methacrylate polymer and anethylcellulose polymer, each of said polymers having a number averagemolecular weight of from about 8000 to about 1×10⁶ and (c) having asubstantially solid or viscoelastic three-dimensional porousinfrastructure having an internal free volume containing a liquid phasefragrance material removably entrapped in said infrastructure, containedin the interstices of said infrastructure and outwardly transportablefrom said infrastructure, each of the components of which fragrancematerial having a C log₁₀ P in the range of from about 1 to about 7, theinitial weight % of fragrance material contained in said plurality ofpolymer particles being from about 0.5% to about 50% by weight of theplurality of polymer particles, each of said fragrance components beingcompatible with said polymer; ii. providing a fabric, hair follicle,mammalian epidermis or solid surface treatment quantity of an aqueouscomposition comprising from about 1% to about 25% by weight of at leastone surfactant which aqueous composition is designed to be in intimatetreatment contact with, in the alternative, (a) at least one fabricarticle over a fabric treatment period of time in a fabric treatmentconcentration and temperature; or (b) at least one solid surface over asolid surface treatment period of time in a solid surface treatmentconcentration and temperature; or (c) at least one hair follicle over ahair follicle treatment period of time in a hair follicle treatmentconcentration and temperature or (d) a mammalian epidermis surface overa mammalian epidermis surface treatment period of time in a mammalianepidermis surface treatment concentration and temperature; iii.providing treatment means for enabling treatment of said fabrics, saidhair follicles, said mammalian epidermis or said solid surfaces; iv.introducing (a) said aqueous composition; (b) said at least one fabricarticle, said at least one hair follicle, said at least one mammalianepidermis or said at least one solid surface; and (c) said plurality ofpolymer particles into said treatment means; v. engaging said treatmentmeans for a treatment period of time at a treatment temperature; vi.disengaging said treatment means; vii. removing (a) said at least onefabric article or (b) said at least one solid surface or (c) said hairfollicles or (d) said mammalian epidermis surface from said treatmentmeans; viii. rinsing (a) said at least one fabric article or (b) said atleast one solid surface or (c) said hair follicles or (d) said mammalianepidermis surface; and ix. drying (a) said at least one fabric articleor (b) said at least one solid surface or (c) said hair follicles or (d)said mammalian epidermis surface wherein fragrance components andmalodour molecules are compatible with said polymers.
 10. The process ofclaim 9 wherein said treatment is a cleaning treatment.
 11. The processof claim 10 wherein said polymer particle infrastructure is composed ofan ethylene-vinyl acetate copolymer.
 12. The process of claim 9 whereinthe treatment means is a laundry washing machine, and the process is forimparting an aesthetically-pleasing fragrance to and substantiallyremoving a perceived malodour from aqueous surfactant-containingcomposition-treated fabrics.
 13. The process of claim 12 wherein saidpolymer particle infrastructure is composed of an ethylene-vinyl acetatecopolymer.
 14. The process of claim 9 operated according to themathematical model system: $\begin{matrix}{{m_{P}{\int_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}\quad{\mathbb{d}\theta}}}} + {m_{W}{\int_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}\quad{\mathbb{d}\theta}}}} +} \\{m_{S}{\int_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}\quad{\mathbb{d}\theta}}}}\end{matrix} = {C_{T}m_{T}}$ for the fragrance composition; and${\sum\limits_{i = 1}^{n}\quad\left( {m_{p} + C_{pi} + {m_{wi}C_{wi}} + {m_{s}C_{si}}} \right)} = {C_{T}m_{T}\quad{for}\quad{``n"}}$individual fragrance components wherein 1≦i≦n; wherein θ represents timein hours; wherein C_(P) represents the fragrance concentration in thepolymer particle in grams/liter; wherein$\frac{\partial C_{P}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the polymer particle withrespect to time, measures in grams/liter-hour; wherein C_(W) representsthe fragrance concentration in the water phase in grams/liter; wherein$\frac{\partial C_{w}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the water phase with respect totime measured in grams/liter-hour; wherein C_(S) represents thefragrance concentration in the surfactant phase in grams/liter; wherein$\frac{\partial C_{S}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the surfactant phase withrespect to time measured in grams/liter-hour; wherein C_(T) representsthe total concentration of fragrance in the system in grams/liter;wherein m_(P) represents the mass of the polymer particles in grams;wherein m_(S) represents the surfactant mass in grams; wherein m_(W)represents the water mass in grams; and wherein m_(T) represents thetotal system mass in gramswith all terms being measured at a point intime, θ.
 15. The process of claim 14 wherein in the mathematical model:${{m_{P}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}d\quad\theta}}} + {m_{W}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}d\quad\theta}}} + {m_{S}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}d\quad\theta}}}} = {C_{T}m_{T}}$C_(P) = −k₁LN(θ + 1) + k₂  with  0.015 ≥ k₁ ≥ 0.03  and  0.18 ≥ k₂ ≥ 0.22;C_(S) = k₃LN(θ + 1) + k₄with  1.5 × 10⁻³ ≥ k₃ ≥ 2.2 × 10⁻³  and  1.2 × 10⁻⁴ ≥ k₄ ≥ 2.0 × 10⁻⁴; andC_(W) = k₅LN(θ + 1) + k₆with  1.5 × 10⁻⁶ ≥ k₅ ≥ 3.0 × 10⁻⁶  and  1.5 × 10⁻⁷ ≥ k₆ ≥ 3.0 × 10⁻⁷16. The process of claim 9 wherein the plurality of polymer particles isproduced by a process comprising the sequential steps of (a) blendingpolymer pellets with fragrance material for a period of time of fromabout 0.05 hours to about 20 hours; (b) extruding the resulting productat a temperature of from about 130° C. to about 170° C. to form anextrudate; (c) cooling the resulting extrudate to a temperature in therange of from about 15° C. to about 40° C. and (d) cryogrinding theresulting extrudate to form cryoground particles.
 17. The process ofclaim 9 wherein the plurality of polymer particles is produced by aprocess comprising the sequential steps of (a) blending polymer pelletswith silicon dioxide and fragrance material for a period of time of fromabout 0.05 hours to about 20 hours; (b) extruding the resulting productat a temperature of from about 130° C. to about 170° C. to form anextrudate; (c) cooling the resulting extrudate to a temperature in therange of from about 15° C. to about 40° C. and (d) cryogrinding theresulting extrudate to form cryoground particles.
 18. The process ofclaim 9 wherein the plurality of polymer particles is produced by aprocess comprising the sequential steps of (a) extruding polymer pelletswith one or more foam forming agents to from a foamed extrudate; (b)cooling the resulting extrudate to form an extrudate tow; (c)particularizing the resulting tow to form microporous polymer particles;and (d) admixing the resulting particles with a fragrance composition,the components of which are compatible with the polymer.
 19. A processfor imparting an aesthetically-pleasing substantive fragrance to and/orsubstantially removing a perceived malodour from aqueoussurfactant-containing composition-treated fabrics, hair follicles,mammalian epidermis or solid surfaces during treatment of said fabricsor hair follicles or mammalian epidermis or said solid surfaces withsurfactant-containing compositions comprising the steps of: i. providinga first plurality of polymer particles (a) having a volume averagediameter of from about 0.01 microns to about 1000 microns, (b) having asolid or viscoelastic infrastructure which is composed of anethylene-vinyl acetate copolymer containing from about 10% to about 90%vinyl acetate monomeric units and having a number average molecularweight of from about 8000 to about 1×10⁶ and (c) having a substantiallysolid or viscoelastic three-dimensional porous infrastructure having afree volume containing a liquid phase fragrance material removablyentrapped in said infrastructure, contained in the interstices of saidinfrastructure and outwardly transportable from said infrastructure,each of the components of which fragrance material having a C log₁₀ P inthe range of from about 1 to about 7, the initial weight % of fragrancematerial contained in said plurality of polymer particles being fromabout 0.5% to about 50% by weight of the plurality of polymer particles,each of said fragrance components being compatible with said polymer;ii. providing a second plurality of polymer particles (a) having avolume average diameter of from about 0.01 microns to about 1000microns, (b) having a solid or viscoelastic infrastructure which iscomposed of an ethylcellulose polymer having a number average molecularweight of from about 8000 to about 1×10⁶ and (c) having a substantiallysolid or viscoelastic three-dimensional porous infrastructuresurrounding a liquid phase fragrance material removably entrapped insaid infrastructure, contained in the interstices of said infrastructureand outwardly transportable from said infrastructure, each of thecomponents of which fragrance material having a C log₁₀ P in the rangeof from about 1 to about 7, the initial weight % of fragrance materialcontained in said plurality of polymer particles being from about 0.5%to about 50% by weight of the plurality of polymer particles; iii.mixing said first plurality of polymer particles with said secondplurality of polymer particles to form a third plurality of polymerparticles; iv. providing a fabric, hair follicle, mammalian epidermis orsolid surface treatment quantity of an aqueous composition comprisingfrom about 1% to about 25% by weight of at least one surfactant whichaqueous composition is designed to be in intimate treatment contact witheither (a) at least one fabric article over a fabric treatment period oftime in a fabric treatment concentration and temperature or (b) at leastone solid surface over a solid surface treatment period of time in asolid surface treatment concentration and temperature or (c) at leastone hair follicle over a hair follicle treatment period of time in ahair follicle treatment concentration and temperature or (d) a mammalianepidermis surface over a mammalian epidermis surface treatment period oftime in a mammalian epidermis surface treatment concentration andtemperature; v. providing treatment means for enabling treatment of saidfabrics, mammalian epidermis, hair follicles or said solid surfaces; vi.introducing (a) said aqueous composition; (b) said at least one fabricarticle, hair follicle, mammalian epidermis or solid surface; and (c)said third plurality of polymer particles into said treatment means;vii. engaging said treatment means for a treatment period of time at atreatment temperature; viii. disengaging said treatment means; ix.removing (a) said at least one fabric article or (b) said at least onesolid surface or (c) said at least one hair follicle or (d) saidmammalian epidermis from said treatment means; x. rinsing (a) said atleast one fabric article or (b) said at least one solid surface or (c)said at least one hair follicle or (d) said mammalian epidermis; and x.drying (a) said at least one fabric article or (b) said at least onesolid surface or (c) said at least one hair follicle or (d) saidmammalian epidermis wherein each of the fragrance components of thefragrance compositions and each of the malodour molecules is compatiblewith the polymers which compose each of the infrastructures of each ofthe polymer particles.
 20. The process of claim 19 wherein the treatmentmeans is a laundry washing machine, and the process is for imparting anaesthetically-pleasing fragrance to and substantially removing aperceived malodour from aqueous surfactant-containingcomposition-treated fabrics.
 21. The process of claim 19 wherein saidtreatment is a cleaning treatment.
 22. The process of claim 19 operatedaccording to the mathematical model system:${{m_{P}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}d\quad\theta}}} + {m_{W}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}d\quad\theta}}} + {m_{S}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}d\quad\theta}}}} = {C_{T}m_{T}}$for the fragrance composition; and${\sum\limits_{i = 1}^{m}\left( {{m_{p}C_{pi}} + {m_{wi}C_{wi}} + {m_{s}C_{si}}} \right)} = {C_{T}m_{T}}$individual fragrance components wherein 1≦i≦n; wherein θ represents timein hours; wherein C_(P) represents the fragrance concentration in thepolymer particle in grams/liter; wherein$\frac{\partial C_{p}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the polymer particle withrespect to time, measures in grams/liter-hour; wherein C_(W) representsthe fragrance concentration in the water phase in grams/liter; wherein$\frac{\partial C_{w}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the water phase with respect totime measured in grams/liter-hour; wherein C_(S) represents thefragrance concentration in the surfactant phase in grams/liter; wherein$\frac{\partial C_{S}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the surfactant phase withrespect to time measured in grams/liter-hour; wherein C_(T) representsthe total concentration of fragrance in the system in grams/liter;wherein m_(P) represents the mass of the polymer particles in grams;wherein m_(S) represents the surfactant mass in grams; wherein m_(W)represents the water mass in grams; and wherein m_(T) represents thetotal system mass in grams with all terms being measured at a point intime, θ.
 23. The process of claim 22 wherein in the mathematical model:${{m_{P}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}d\quad\theta}}} + {m_{W}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}d\quad\theta}}} + {m_{S}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}d\quad\theta}}}} = {C_{T}m_{T}}$C_(P) = −k₁LN(θ + 1) + k₂  with  0.015 ≥ k₁ ≥ 0.03  and  0.18 ≥ k₂ ≥ 0.22;C_(S) = k₃LN(θ + 1) + k₄with  1.5 × 10⁻³ ≥ k₃ ≥ 2.2 × 10⁻³  and  1.2 × 10⁻⁴ ≥ k₄ ≥ 2.0 × 10⁻⁴; andC_(W) = k₅LN(θ + 1) + k₆with  1.5 × 10⁻⁶ ≥ k₅ ≥ 3.0 × 10⁻⁶  and  1.5 × 10⁻⁷ ≥ k₆ ≥ 3.0 × 10⁻⁷.24. The process of claim 19 wherein the liquid phase fragrance materialis selected from the group consisting of dihydromyrcenol,p-t-butyl-α-methylhydrocinnamaldehyde, a mixture ofhexahydro-4,7-methanoinden-5-yl acetate andhexahydro-4,7-methanoinden-6-yl acetate,2,4-dimethyl-3-cyclohexene-1-carboxaldehyde,3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, n-hexylsalicylate, the methyl ester of 3-oxo-2-n-pentylcyclopentane acetic acidand α-methyl-3,4-methylenedioxyhydrocinnamaldehyde, the ethylene-vinylacetate copolymer contains 65-75% ethylene moieties and 25-35% vinylacetate moieties, the fragrance composition component free energies ofmixing in the ethylene-vinyl acetate copolymer is in accordance withFIG. 8 and the fragrance composition component free energies of mixingin the ethyl cellulose polymer is in accordance with FIG.
 12. 25. Theprocess of claim 24 operated according to the mathematical model system:${{m_{P}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}d\quad\theta}}} + {m_{W}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}d\quad\theta}}} + {m_{S}{\int\limits_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}d\quad\theta}}}} = {C_{T}m_{T}}$for the fragrance composition; and${\sum\limits_{i = 1}^{m}\left( {{m_{p}C_{pi}} + {m_{wi}C_{wi}} + {m_{s}C_{si}}} \right)} = {C_{T}m_{T}}$individual fragrance components wherein 1≦i≧n; wherein θ represents timein hours; wherein C_(P) represents the fragrance concentration in thepolymer particle in grams/liter; wherein$\frac{\partial C_{p}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the polymer particle withrespect to time, measures in grams/liter-hour; wherein C_(W) representsthe fragrance concentration in the water phase in grams/liter; wherein$\frac{\partial C_{w}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the water phase with respect totime measured in grams/liter-hour; wherein C_(S) represents thefragrance concentration in the surfactant phase in grams/liter; wherein$\frac{\partial C_{S}}{\partial\theta}$ represents the partialderivative of fragrance concentration in the surfactant phase withrespect to time measured in grams/liter-hour; wherein C_(T) representsthe total concentration of fragrance in the system in grams/liter;wherein m_(P) represents the mass of the polymer particles in grams;wherein m_(S) represents the surfactant mass in grams.; wherein m_(W)represents the water mass in grams; and wherein m_(T) represents thetotal system mass in grams with all terms being measured at a point intime, θ.
 26. The process of claim 25 wherein in the mathematical model:${{m_{P}{\int_{0}^{\theta}{\left( \frac{\partial C_{P}}{\partial\theta} \right)_{C_{S},C_{W}}{\mathbb{d}\theta}}}} + {m_{W}{\int_{0}^{\theta}{\left( \frac{\partial C_{W}}{\partial\theta} \right)_{C_{P},C_{S}}{\mathbb{d}\theta}}}} + {m_{S}{\int_{0}^{\theta}{\left( \frac{\partial C_{S}}{\partial\theta} \right)_{C_{P},C_{W}}{\mathbb{d}\theta}}}}} = {C_{T}m_{T}}$$\begin{matrix}{{C_{P} = {{{{- k_{1}}{{LN}\left( {\theta + 1} \right)}} + {k_{2}\quad{with}\quad 0.015}} \geq k_{1} \geq {0.03\quad{and}\quad 0.18} \geq k_{2} \geq 0.22}};} \\{C_{S} = {{{k_{3}{{LN}\left( {\theta + 1} \right)}} + {k_{4}\quad{with}\quad 1.5 \times 10^{- 3}}} \geq k_{3} \geq {2.2 \times 10^{- 3}\quad{and}}}} \\{{{1.2 \times 10^{- 4}} \geq k_{4} \geq {2.0 \times 10^{- 4}}};\quad{and}} \\{C_{W} = {{{k_{5}{{LN}\left( {\theta + 1} \right)}} + {k_{6}\quad{with}\quad 1.5 \times 10^{- 6}}} \geq k_{5} \geq {3.0 \times 10^{- 6}\quad{and}}}} \\{{1.5 \times 10^{- 7}} \geq k_{6} \geq {3.0 \times {10^{- 7}.}}}\end{matrix}$
 27. An aqueous treatment composition comprising aplurality of polymer particles (a) having a volume average diameter offrom about 0.01 microns to about 1000 microns; (b) having a solid orviscoelastic infrastructure which is composed of a substance selectedfrom the group consisting of an ethylene-vinyl acetate copolymercontaining from about 10% to about 90% vinyl acetate monomeric units, anethylcellulose polymer, a polystyrene polymer and a polymethylmethacrylate polymer, each of said polymers having a number averagemolecular weight of from about 8000 to about 1×10⁶ and (c) having asubstantially solid or viscoelastic three-dimensional porousinfrastructure surrounding a free volume; suspended in an aqueouscomposition comprising from about 1% to about 25% by weight of at leastone surfactant.
 28. The composition of claim 27 wherein the free volumeof the polymer contains a fragrance composition, each of the componentsof which is compatible with said polymer.
 29. The composition of claim27 wherein the plurality of polymer particles comprises (a) particleshaving infrastructures composed of ethylene-vinyl acetate copolymers and(b) particles having infrastructures composed of ethyl cellulose. 30.The composition of claim 29 wherein the free volumes of theethylene-vinyl acetate polymer particles and the ethylcelluloseparticles each contain fragrance compositions, the components of whichare each compatible with said ethyl cellulose and said ethylene-vinylacetate copolymer.
 31. A process for imparting an aesthetically-pleasingsubstantive fragrance to, and/or substantially removing or covering aperceived malodour from one or more solid or semi-solid surfacescomprising the steps of: i. providing a plurality of solid and/orviscoelastic polymer particles (a) having a volume average diameter offrom about 0.01 microns to about 1000 microns; (b) having a solidinfrastructure which is composed of a substance selected from the groupconsisting of an ethylene-vinyl acetate copolymer containing from about10% to about 90% vinyl acetate monomeric units, an ethylcellulosepolymer, a polystyrene polymer and a polymethyl methacrylate polymer,each of said polymers having a number average molecular weight of fromabout 8000 to about 1×10⁶ and (c) having a substantially solid orviscoelastic three-dimensional porous infrastructure surrounding a freevolume; ii. optionally including in the solid or viscoelasticinfrastructure free volume a fragrance composition, each of thecomponents of which is compatible with said polymer; iii. effectingdeposition of said plurality of polymer particles onto said surfacewherein fragrance components and malodour molecules are compatible withsaid polymer.
 32. The process of claim 1 wherein each of theinfrastructures of each of the polymer particles comprises, in addition,a solvent.
 33. The process of claim 32 wherein the solvent is selectedfrom the group consisting of isopropyl myristate, diethyl phthalate,dibutyl phthalate, diisopropyl adipate, benzyl benzoate, mineral oil, amethyl ester of a vegetable-derived C₁₂-C₁₈ carboxylic acid and aglyceryl ester of a vegetable-derived C₁₀ carboxylic acid.
 34. Theprocess of claim 19 wherein each of the infrastructures of each of thepolymer particles comprises, in addition, a solvent.
 35. The process ofclaim 34 wherein the solvent is selected from the group consisting ofisopropyl myristate, diethyl phthalate, dibutyl phthalate, diisopropyladipate, benzyl benzoate, mineral oil, a methyl ester of avegetable-derived C₁₂-C₁₈ carboxylic acid and a glyceryl ester of avegetable-derived C₁₀ carboxylic acid.
 36. The process of claim 31wherein each of the infrastructures of each of the polymer particlescomprises, in addition, a solvent.
 37. The process of claim 36 whereinthe solvent is selected from the group consisting of isopropylmyristate, diethyl phthalate, dibutyl phthalate, diisopropyl adipate,benzyl benzoate, mineral oil, a methyl ester of a vegetable-derivedC₁₂-C₁₈ carboxylic acid and a glyceryl ester of a vegetable-derived C₁₀carboxylic acid.
 38. The process of claim 1 wherein each of theinfrastructures of each of the polymer particles comprises, in addition,a filler.
 39. The process of claim 38 wherein the filler is selectedfrom the group consisting of SiO₂, CaCO₃, MgCO₃, Al₂O₃, MgO, ZnO, TiO₂,surface-modified silicas, hydrated alkali metal-aluminum silicates,CaSO₄.2H₂O, clays, modified clays, wood flour and activated carbon. 40.The process of claim 19 wherein each of the infrastructures of each ofthe polymer particles comprises, in addition, a filler.
 41. The processof claim 40 wherein the filler is selected from the group consisting ofSiO₂, CaCO₃, MgCO₃, Al₂O₃, MgO, ZnO, TiO₂, surface-modified silicas,hydrated alkali metal-aluminum silicates, CaSO_(40.2)H₂O, clays,modified clays, wood flour and activated carbon.
 42. The process ofclaim 31 wherein each of the infrastructures of each of the polymerparticles comprises, in addition, a filler.
 43. The process of claim 42wherein the filler is selected from the group consisting of SiO₂, CaCO₃,MgCO₃, Al₂O₃, MgO, ZnO, TiO₂, surface-modified silicas, hydrated alkalimetal-aluminum silicates, CaSO_(40.2)H₂O, clays, modified clays, woodflour and activated carbon.
 44. A polymethyl methacrylate particlecomposition consisting of free volume-containing polymethyl methacrylateparticles which are capable of absorbing compatible fragrancecomposition components and malodour molecules produced according to theprocess comprising the steps of: (a) milling polymethyl methacrylate toprovide polymethyl methacrylate particles having an average effectivediameter in the range of from about 5 microns to about 100 millimeters;and (b) admixing the resulting milled particles with a plasticizingquantity of a plasticizing composition selected from the groupconsisting of lower alkanols and lower alkanones or greater than about10% aqueous solutions thereof for a time period of from about 30 secondsto about 10 minutes thereby forming plasticized polymer particles. 45.The polymethyl methacrylate particle composition of claim 44 wherein inthe process for producing said composition, the resulting plasticizedpolymer particles are admixed with a fragrance material which iscompatible with the polymethyl methacrylate, whereby from about 0.5% toabout 50% by weight of the filled particle of fragrance is absorbed intoeach of the free volumes of each of the polymer particles.
 46. Thepolymethyl methacrylate particle composition of claim 44 wherein in theprocess for producing said composition, the resulting plasticizedpolymer particles are separated from the plasticizing compound, and thethus-separated particles are then admixed with a fragrance materialwhich is compatible with the polymethyl methacrylate, whereby from about0.5% to about 50% by weight of the filled particle of fragrance isabsorbed into each of the free volumes of each of the polymer particles.47. The composition of claim 27 wherein the infrastructure of each of aplurality of the polymeric particles is composed of polymethylmethacrylate and wherein the polymethyl methacrylate polymer particlesare produced according to the process comprising the steps of: (a)milling polymethyl methacrylate to provide polymethyl methacrylateparticles having an average effective diameter in the range of fromabout 5 microns to about 100 millimeters.; and (b) admixing theresulting milled particles with a plasticizing quantity of aplasticizing compound selected from the group consisting of loweralkanols and lower alkanones or greater than 10% aqueous solutionsthereof for a time period of from about 30 seconds to about 10 minutesthereby forming plasticized polymer particles.
 48. The composition ofclaim 47 wherein in the process for producing the polymethylmethacrylate polymer particle composition, the resulting plasticizedpolymer particles are admixed with a fragrance material which iscompatible with the polymethyl methacrylate, whereby from about 0.5% toabout 50% by weight of the filled particle of fragrance is absorbed intoeach of the free volumes of each of the polymer particles.
 49. Thecomposition of claim 47 wherein in the process for producing thepolymethyl methacrylate polymer particle composition, the resultingplasticized polymer particles are separated from the plasticizingcompound, and the thus-separated particles are then admixed with afragrance material which is compatible with the polymethyl methacrylate,whereby from about 0.5% to about 50% by weight of the filled particle offragrance is absorbed into each of the free volumes of each of thepolymer particles.
 50. The process of claim 1 wherein at least a finiteportion of the polymeric particles are polymethyl methacrylate polymerparticles produced according to the process comprising the steps of: (a)milling polymethyl methacrylate to provide polymethyl methacrylateparticles having an average effective diameter in the range of fromabout 5 microns to about 100 millimeters; and (b) admixing the resultingmilled particles with a plasticizing quantity of a plasticizing compoundselected from the group consisting of lower alkanols and lower alkanonesor greater than about 10% aqueous solutions thereof for a time period offrom about 30 seconds to about 10 minutes thereby forming plasticizedpolymer particles.
 51. The process of claim 31 wherein at least a finiteportion of the polymeric particles are polymethyl methacrylate polymerparticles produced according to the process comprising the steps of: (a)milling polymethyl methacrylate to provide polymethyl methacrylateparticles having an average effective diameter in the range of fromabout 5 microns to about 100 millimeters.; and (b) admixing theresulting milled particles with a plasticizing quantity of aplasticizing compound selected from the group consisting of loweralkanols and lower alkanones or greater than about 10% aqueous solutionsthereof for a time period of from about 30 seconds to about 10 minutesthereby forming plasticized polymer particles.
 52. The process of claim50 wherein in the process for producing the polymethyl methacrylatepolymer particle composition, the resulting plasticized polymerparticles are separated from the plasticizing compound, and thethus-separated particles are then admixed with a fragrance materialwhich is compatible with the polymethyl methacrylate, whereby from about0.5% to about 50% by weight of the filled particle of fragrance isabsorbed into each of the free volumes of each of the polymer particles.53. The process of claim 51 wherein in the process for producing thepolymethyl methacrylate polymer particle composition, the resultingplasticized polymer particles are separated from the plasticizingcompound, and the thus-separated particles are then admixed with afragrance material which is compatible with the polymethyl methacrylate,whereby from about 0.5% to about 50% by weight of the filled particle offragrance is absorbed into each of the free volumes of each of thepolymer particles.
 54. The polymethyl methacrylate particle compositionof claim 44 wherein in the process for producing the particles, theplasticizing composition is an aqueous solution of ethanol.
 55. Thecomposition of claim 48 wherein in the process for producing theparticles, the plasticizing composition is an aqueous solution ofethanol.
 56. The process of claim 52 wherein in the process forproducing the particles, the plasticizing composition is an aqueoussolution of ethanol.
 57. The polymethyl methacrylate composition ofclaim 54 wherein in the process for producing the particles, theplasticizing composition is 50% aqueous ethanol.
 58. The composition ofclaim 48 wherein in the process for producing the particles, theplasticizing composition is a 50% aqueous solution of ethanol.
 59. Theprocess of claim 52 wherein in the process for producing the particles,the plasticizing composition is a 50% aqueous solution of ethanol.